KR20140048324A - Silylated polybutadiene - Google Patents

Abstract

(식 중, R¹, R², 및 R³ 은 각각 독립적으로, 비치환 또는 치환기를 갖는 아릴기, 알킬기, 또는 아르알킬기를 나타낸다. 단, R¹ ~ R³ 중에서 적어도 1 개는 아릴기 또는 아르알킬기이다.) 로 나타내는 반복 단위를 함유하는 것을 특징으로 하는 실릴화 폴리부타디엔, 상기 실릴화 폴리부타디엔과 중합 개시제를 함유하는 것을 특징으로 하는 경화성 조성물, 그리고 상기 경화성 조성물을 경화시켜 얻어진 경화물을 제공한다.An object of the present invention is to provide a derivative of polybutadiene which is suitable as a material of a curable composition for obtaining a cured product having a high shear force. The present invention is the following formula (I)

(Wherein, R ¹ , R ² , and R ³ each independently represent an aryl group, an alkyl group, or an aralkyl group having an unsubstituted or substituted group, provided that at least one of R ¹ to R ³ is an aryl group or A silylated polybutadiene, the said silylated polybutadiene and a polymerization initiator are contained, and the cured | curing material obtained by hardening | curing the said curable composition is contained. to provide.

Description

Silylate polybutadiene {SILYLATED POLYBUTADIENE}

The present invention relates to polybutadiene in which a part of polybutadiene is silylated and a curable composition thereof.

This application claims priority in October 6, 2011 based on Japanese Patent Application No. 2011-221960 for which it applied to Japan, and uses the content for it here.

Conventionally, the polybutadiene which silylated a part of double bond of a side chain is known. For example, in patent document 1, the curable composition containing the polybutadiene to which the silyl group was added to a part of carbon-carbon double bond of a side chain, and a carbonaceous material is proposed. Specifically, a curable composition containing polybutadiene obtained by triethylsilylating 20.5% or 25.2% of the side-chain carbon-carbon double bonds is disclosed. Since the hardened | cured material obtained from the said curable composition is excellent in hot water resistance, electroconductivity, etc., the use as a fuel cell separator, an electrode, an electromagnetic shield, a heat radiation material, a battery integrated body, etc. is proposed.

Patent Document 1: Japanese Unexamined Patent Publication No. 2005-344110

On the other hand, higher adhesiveness is calculated | required with respect to the hardened | cured material which hardened the curable composition containing polybutadiene and its derivative (s). However, about the curable composition containing the polybutadiene in which a part of the double bond of a side chain is silylated, the hardened | cured material which has a high shear force suitable as an adhesive agent until now has not been obtained.

Then, an object of this invention is to provide the derivative of polybutadiene which is suitable as a material of curable composition for obtaining the hardened | cured material which has high shear force.

Moreover, in the field of thin film materials, the thin film material which has a high refractive index was calculated | required. It is another object of the present invention to provide a thin film material having a high refractive index.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, it discovered that the curable composition excellent in shearing force is obtained by using the polymer which added the silyl group in the fixed ratio to the double bond of the side chain of polybutadiene. Moreover, it discovered that the thin film material obtained by hardening such a polymer has high refractive index, and came to complete this invention.

That is, this invention provides the following (1)-(8).

(1)

However,

(In formula (I), R <^1> , R <^2> and R <^3> respectively independently represents an aryl group, an alkyl group, or an aralkyl group which has an unsubstituted or substituent. However, at least 1 is an R <^1> -R <^3> A silylated polybutadiene containing a repeating unit represented by an aryl group or an aralkyl group.).

(2) The silylated polybutadiene as described in said (1) containing 1-50 mol% of all the repeating units represented by said Formula (I).

(3) A polybutadiene obtained by silylating a repeating unit represented by 75 to 100 mol% of the following formula (II) and a repeating unit represented by 0 to 25 mol% of the following formula (III): (1) Or silylated polybutadiene according to (2).

[Figure 2]

(4) The silylated polybutadiene according to any one of the above (1) to (3), wherein the number average molecular weight is 500 to 10,000.

(5) The curable composition containing the silylated polybutadiene as described in any one of said (1)-(4), and a polymerization initiator.

(6) Hardened | cured material obtained by hardening | curing the curable composition as described in said (5).

(7) The silylated polybutadiene as described in any one of said (1)-(4) and a polymerization initiator are contained, The adhesive agent characterized by the above-mentioned.

(8) The composition for thin film formation containing the silylated polybutadiene in any one of said (1)-(4), and a polymerization initiator.

The curable composition containing the silylated polybutadiene of the present invention has excellent shear force as the cured product. For this reason, the said curable composition is useful as various adhesive materials, such as a solvent-type adhesive agent and a two-component acrylic adhesive, etc., and thin film materials, such as various coating films. Moreover, the thin film obtained by hardening | curing the curable composition containing the silylated polybutadiene of this invention has a high refractive index.

<Silylated polybutadiene>

The silylated polybutadiene of the present invention is characterized by containing a repeating unit represented by the following formula (I). The ratio of the repeating unit represented by Formula (I) contained in all the repeating units is not specifically limited. It is preferable to contain 1-30 mol% of repeating units represented by Formula (I) from a viewpoint that the hardened | cured material obtained by hardening | curing a curable composition has high adhesiveness among all the repeating units. It is preferable to contain 1-50 mol% of all the repeating units in the repeating unit represented by Formula (I) from a viewpoint that the hardened | cured material obtained by hardening | curing a curable composition has a high refractive index. In formula (I), R <^1> , R <^2> and R <^3> respectively independently represents an aryl group, an alkyl group, or an aralkyl group which has an unsubstituted or substituent. Provided that at least one of R ¹ to R ³ is an aryl group or an aralkyl group.

[Figure 3]

The aryl group in R ¹ , R ² , or R ³ may be a monocyclic aryl group or a polycyclic aryl group. Specifically, a phenyl group, 1-naphthyl group, 2-naphthyl group, etc. are mentioned, A phenyl group is preferable.

The number of R ^1, R substituent having an aryl group at the ^2, or R ³ is not particularly limited, R ^1, R ^2, or R ³ is a substituent, each independently, and may have a substituent of 1, 2 or more You may have it.

As a substituent which the aryl group in R <^1> , R <^2> , or R <^3> has specifically, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a cyano group, a nitro group, an alkyl group, an alkoxy group, an aryl group, etc. Can be mentioned. As the alkyl group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, C1-C6 linear or branched group, such as n-hexyl group, is mentioned. As an alkoxy group, C1-C4, such as a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, etc. The linear or branched group of may be mentioned. As an aryl group, monocyclic or bicyclic groups, such as a phenyl group, 1-naphthyl group, and 2-naphthyl group, are mentioned, for example. As a substituent which the aryl group in R <^1> , R <^2> or R <^3> has, it is preferable that it is an alkyl group or an alkoxy group, and it is a C1-C6 linear or branched alkyl group, or a C1-C4 linear or branched thing. It is more preferable that it is a chain alkoxy group.

The alkyl group in R ¹ , R ² , or R ³ means a linear or branched alkyl group having 1 to 20 carbon atoms. As the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, octyl group Etc. can be mentioned.

As a substituent which the alkyl group in R <^1> , R <^2> or R <^3> has, the same thing as what was mentioned as a substituent which an aryl group has is mentioned.

The aralkyl group in R ¹ , R ² , or R ³ means a group in which the aryl and the alkyl are bonded, such as benzyl, 1-phenylethyl, 2-phenylethyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like. Can be mentioned.

Moreover, all the aryl groups, alkyl groups, and aralkyl groups in R <^1> , R <^2> or R <^3> may be the same group, and may be a separate group, respectively. As the silylated polybutadiene of the present invention, R ¹ , R ² , and R ³ are each independently an unsubstituted or aryl group having a substituent, more preferably an unsubstituted or phenyl group having a substituent, and R ¹ , It is more preferable that R ² and R ³ are all unsubstituted or a phenyl group having an alkyl group or an alkoxy group as a substituent, and it is particularly preferable that R ¹ , R ² , and R ³ are all unsubstituted phenyl groups.

By containing the repeating unit represented by Formula (I), the silylated polybutadiene of this invention shows the high shear force of the hardened | cured material, and the cured film shows the high refractive index. 1-50 mol% is preferable, as for the content rate of the repeating unit represented by Formula (I) with respect to all the repeating units of the silylated polybutadiene of this invention, 1-30 mol% is more preferable, 1-25 mol% is further more It is preferable, 1-20 mol% is further more preferable, 1-15 mol% is especially preferable, 1-10 mol% is more especially preferable, and 2-9 mol% is the most preferable.

In addition to the repeating unit represented by Formula (I), the silylated polybutadiene of this invention contains 1 or more types chosen from the group which consists of a repeating unit represented by following formula (II) and a repeating unit represented by following formula (III). desirable. As for the double bond in Formula (II) and Formula (III), one part may be hydrogenated (it becomes saturated carbon-carbon bond by hydrogenation). The double bond in formula (III) may be either a cis bond or a trans bond, and in one molecule of silylated polybutadiene, the repeating unit in formula (III) and the repeating unit in formula (III) The repeating unit whose double bond is a trans bond may be mixed.

[Figure 4]

As a silylated polybutadiene of this invention, it is preferable that the sum of the repeating unit represented by Formula (I) and the repeating unit represented by Formula (II) is 75-100 mol% among all the repeating units, and it is more preferable that it is 80-100 mol%. desirable. Moreover, as a silylated polybutadiene of this invention, it is preferable that the repeating unit represented by Formula (III) is 0-25 mol% among all the repeating units, and it is more preferable that it is 0-20 mol%.

There is no restriction | limiting in particular in the terminal structure of the silylated polybutadiene in this invention, The thing which modified the structure of the polymer terminal in various ways can be used. Specific examples thereof include, but are not limited to, those in which the terminal is modified with a hydroxyl group, the terminal is acrylic-modified, the terminal is methacryl-modified, and the terminal is modified with a carboxylic acid group. .

The molecular weight of the silylated polybutadiene of the present invention is not particularly limited. As silylated polybutadiene of this invention, it is preferable that the number average molecular weights (Mn) by GPC (gel permeation chromatography) method which used polystyrene as an index are 500-10,000, and it is more preferable that it is 1,000-5,000.

 The dispersity (Mw / Mn) of the silylated polybutadiene of the present invention is preferably 1.01 to 4.00, more preferably 1.01 to 3.00, still more preferably 1.01 to 2.50.

<Method for producing silylated polybutadiene>

The silylated polybutadiene of the present invention may be produced by any method. For example, it can manufacture by making polybutadiene and the silane compound represented by following formula (IV) react in presence of a catalyst.

[Figure 5]

In formula (IV), R <^1> , R <^2> or R <^3> is the same as that of the said Formula (I). Specific examples of the silane compound represented by formula (IV) include triphenylsilane, tris (4-methylphenyl) silane, tris (4-ethoxyphenyl) silane, dimethylphenylsilane, ethylmethylphenylsilane, diethylphenylsilane, and the like. Among them, triphenylsilane is more preferable.

Although it is preferable that 1 mol% or more of all the repeating units is a repeating unit represented by Formula (II), the polybutadiene which makes a silane compound react is not specifically limited. As a raw material of the silylated polybutadiene of this invention, in addition to the repeating unit represented by Formula (II), it is preferable to contain the repeating unit represented by Formula (III), and is represented by 75-100 mol% of Formula (II) It is more preferable that it is polybutadiene which consists of a repeating unit and the repeating unit represented by 0-25 mol% of Formula (III).

Specifically as polybutadiene which consists of a repeating unit represented by 75-100 mol% of Formula (II), and a repeating unit represented by 0-25 mol% of Formula (III), NISSO-PB B-1000 and NISSO-PB B-2000 , NISSO-PB B-3000 (above, Nippon Soda Co., Ltd.), etc. can be illustrated.

The amount of the silane compound used for the silylation reaction can be appropriately determined depending on how many mol% of all the repeat units in the polybutadiene are silylated. It is preferable to use 1 mol of the silane compound per 1 mol of the repeating unit to be silylated. Moreover, you may use an excess amount of a silane compound with respect to 1 mol of repeating units to be silylated. In the case of using an excess amount of silane compound, the desired silylated polybutadiene can be obtained by stopping the reaction at the point when the reaction proceeds up to the desired silylation rate.

The catalyst used for the silylation reaction is not particularly limited as long as there is activity against the hydrosilylation reaction, but a platinum catalyst is preferred. Platinum catalysts include platinum-olefin complexes, platinum-vinylsiloxane complexes, hexachloroplatinum (IV) acids and the like.

Although the reaction temperature of a silylation reaction is not specifically limited, 50-150 degreeC is preferable and 80 degreeC-130 degreeC is more preferable. The reaction time of the silylation reaction is not particularly limited and can be appropriately determined in consideration of the desired silylation rate.

The solvent used for the silylation reaction is not particularly limited as long as the solvent in which polybutadiene is dissolved. Specific examples thereof include nonpolar solvents such as toluene, xylene, ethylbenzene, cyclohexane, hexane, benzene, diethyl ether, and chloroform. Of these, benzene, toluene, xylene, and ethylbenzene are preferable.

When the silylation reaction is carried out under such conditions, the silane compound is added not to the main chain double bond of 1, 4-bond but to the side chain double bond of 1, 2-bond. In addition, the silylation reaction to the double bond of the side chain proceeds to the anti-Markovnikov type.

There is no restriction | limiting in particular in the method of confirming the microstructure of the synthesized silylated polybutadiene, You may confirm by any method. For example, it can be performed by nuclear magnetic resonance method (hereinafter abbreviated as "NMR method") or Fourier transform infrared spectroscopy (hereinafter abbreviated as "FT-IR method"). These specific techniques are described in, for example, the terms of `` Measurement of Polybutadiene's Microstructure by Infrared Spectrum '' in `` Experimental Method of Polymer Synthesis (issued by Chemical Co., Ltd., March 1, 1984, Issue 8) ''. (Page 45), or `` Measurement of the Microstructure of Polybutadiene by Experimental Example 225 NMR '' in `` Experimental Method of Polymer Synthesis (Issued March 1, 1984, Issue 8) '' (Page 49) In addition, it is described in the section (page 51) of "Measurement of the polystructure of polyisoprene by Experimental Example 226 NMR" of "Experimental method of polymer synthesis (Issuance of the 8th chain, issued March 1, 1984)". .

<Curable composition and hardened | cured material>

Curable composition is obtained by adding the other component for hardening silylated polybutadiene to the silylated polybutadiene of this invention.

In addition, in this invention and this specification, the composition before hardening is called curable composition, and what hardened | cured the curable composition is called hardened | cured material.

The curable composition of this invention contains the silylated polybutadiene of this invention and a polymerization initiator, It is characterized by the above-mentioned. The curable composition of this invention may contain only one type of silylated polybutadiene of this invention, and may mix and contain two or more types from which a composition differs.

Although it does not specifically limit as a polymerization initiator contained in the curable composition of this invention, It is preferable that it is a thermal polymerization initiator or a photoinitiator.

As a thermal polymerization initiator, peroxides, such as an inorganic peroxide and an organic peroxide, are mentioned. In addition, a peroxide may be contained individually by 1 type in the curable composition of this invention, and may contain 2 or more types of mixtures.

Examples of the inorganic peroxides include hydrogen peroxide and peracetic acid.

Examples of the organic peroxides include hydroperoxides such as t-butyl hydroperoxide, p-mentane hydroperoxide, cumene hydroperoxide and diisopropylbenzene hydroperoxide; t-butyl peroxylaurate and t-butyl peroxybenzo Peroxy esters such as acetate and t-butylperoxy decanoate; peroxy ketals such as 1,5-di-t-butylperoxy-3, 3, and 5-trimethylcyclohexane; ethyl peroxide Ketone peroxides, such as these; Daacyl peroxides, such as benzoyl peroxide, etc. are mentioned. In addition, benzoin, benzoin isopropylpropyl, benzoin isobutyl ether, 2, 2- diethoxy acetophenone, 2, 2- dimethoxyphenyl acetophenone, 2-ethyl anthraquinone, 1, 3-di ( tert-butyldioxycarbonyl) benzophenone, 4,4'-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis ( 2, 4, 5-triphenyl) imidazole, 2, 2-dimethoxy-1, 2-diphenylethan-1-one (brand name Irgacua 651, Chiba Specialty Chemicals Co., Ltd.), 1 -Hydroxy-cyclohexyl-phenyl-ketone (brand name Irgacua 184, Chiba Specialty Chemicals, Inc.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane -1-one (brand name Irgacure 369, Chiba Specialty Chemicals Co., Ltd.), bis (η ⁵ -2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro -3- (1H-pyrrole-1-yl) -phenyl) titanium) (brand name Irgacua 784, Chiba special Chemicals Co., Ltd., dicumyl peroxide (DCP), t-butylperbenzoate (TBPB), t-butylperoxyhexine-3 (t-butylperoxyhexyne-3) Etc. can be mentioned.

Examples of the photopolymerization initiator include benzophenone, p, p'-diethylaminobenzophenone, benzoin isopropyl ether, benzyl dimethyl ketal and benzyl dimethyl acetal (trade name Irgacua 651; manufactured by Chiba-Geigi Co., Ltd.), Irgacua 184, Ir. And CQ 907 (all manufactured by Chiba-Geigy Co., Ltd.), diethyl thioxanthone, camphor quinone, p-dimethylaminochalcone, carbonylbis (diethylaminocoumarin), and the like.

The content of the polymerization initiator in the curable composition of the present invention is not particularly limited as long as it is an amount capable of sufficiently curing the silylated polybutadiene. As content of the polymerization initiator in the curable composition of this invention, 0.1-30 mass parts is preferable with respect to 100 mass parts of silylated polybutadiene, and 0.5-30 mass parts is more preferable.

The curable composition of this invention may contain a polymeric vinyl compound further. Although hardening reaction can be performed only by a silylated polybutadiene and a polymerization initiator, hardening reaction can also be performed even if it adds a polymeric vinyl compound further.

As a polymerizable vinyl compound, aromatic vinyl compounds, such as styrene, vinyltoluene, (alpha) -methylstyrene, and divinylbenzene; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, t-butyl (meth) acrylate, (meth N-hexyl acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, ( Mono or di (meth) acrylate of poly) ethylene glycol, mono or di (meth) acrylate of (poly) propylene glycol, mono- or di (meth) acrylate of 1,4-butanediol, mono of trimethylolpropane -Unsaturated carboxylic acid esters such as di- or tri- (meth) acrylate; diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, triallyl trimellitate, o, o'- Diallylbisphenol A, o, o'- Allylbisphenol F, 1, 1, 1, 3, 3, 3-hexafluoro-2, 2-bis (p-hydroxy-o-allylphenyl) propane, allylated phenol novolac, 1, 1, 3- Allylides such as tris (4-hydroxyphenyl) propane, 1, 1, 2, 2-tetra (4-hydroxyphenyl) ethane, dehydrating condensates of phenols and hydroxybenzaldehyde; (poly) ethylene glycol di (meth (Poly) oxyalkylene glycol di (meth) acrylates such as) acrylate and (poly) propylene glycol di (meth) acrylate; terminals such as TEA-1000, TE-1000 and TEAI-1000 (manufactured by Nippon Soda) Acrylic modified polybutadiene etc. are mentioned. Moreover, conjugated diene compounds, such as butadiene, isoprene, and chloroprene, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, glycidyl methacrylate, vinylpyridine, diethylaminoethyl acrylate, N-methylmethacrylamide, and acrylo Reactive functional group containing compounds, such as a nitrile, are mentioned. These polymerizable vinyl compounds may be contained in the curable composition of this invention individually by 1 type, and may contain 2 or more types of mixtures.

Various additives can be arbitrarily mix | blended with the curable composition of this invention in the range which does not impair the effect of this invention for various purposes, such as adhesive improvement, refractive index improvement, or solution characteristic improvement. As said additive, a thermosetting resin, a thermoplastic resin, a photocurable resin, antioxidant, a ultraviolet absorber, a leveling agent, an antifoamer, a thickener, a flame retardant, a filler, a plasticizer, a pigment, an antistatic agent, a solvent, etc. are mentioned, for example.

As a thermosetting resin, For example, novolak-type phenol resins, such as a phenol novolak resin, a cresol novolak resin, bisphenol A novolak resin, phenol resins, such as a resolphenol resin, bisphenol A epoxy resin, bisphenol F epoxy resin, etc. Type epoxy resins, novolac epoxy resins, novolac epoxy resins such as cresol novolac epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, triphenol methane type epoxy resins, alkyl modified triphenol methane type epoxy resins, Epoxy resins, such as a azine core containing epoxy resin and a dicyclopentadiene modified phenol type epoxy resin, resin which has triazine rings, such as urea (urea) resin and melamine resin, unsaturated polyester resin, bismaleimide resin, and polyurethane resin , Diallyl phthalate resin, silicone resin, resin having benzoxazine ring, cyanate ester resin and the like Can be used.

As the thermoplastic resin, for example, aromatic or aliphatic petroleum resin, rosin resin, terpene resin, coumarone resin, xylene resin, ketone resin, or the like can be used.

As the photocurable resin, for example, an ultraviolet curable resin mainly containing an acrylic compound, a urethane acrylate oligomer or a polyester urethane acrylate oligomer, an ultraviolet curable resin having an main component, an epoxy resin, a vinylphenol resin, or the like can be used. .

As antioxidant, 2, 6-di-t- butyl- 4-methyl phenol, n-octadecyl-3- (4'-hydroxy-3 ', 5'- di-t- butylphenyl) prop Cypionate, 2, 2'-methylenebis (4-methyl-6-t-butylphenol), 2, 2'-methylenebis (4-ethyl-6-t-butylphenol), 2, 4-bis [( Octylthio) methyl] -0-cresol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-di-t- Amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenylacrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentyl Phenyl)] Hindered phenol-type antioxidants, such as an acrylate; Sulfur type | system | groups, such as a dilauryl thiodipropionate and a lauryl stearyl thiodipropionate pentaerythritol- tetrakis ((beta) -laurylthio propionate) Antioxidant; Phosphorus antioxidant, such as a tris (nonylphenyl) phosphite and a tris (2, 4-di-t- butylphenyl) phosphite, etc. can be used.

As an ultraviolet absorber, For example, salicylic acids, such as phenyl salicylate, butylphenyl salicylate, and octylphenyl salicylate; dihydroxy benzophenone, hydroxy methoxy benzophenone, hydroxy octoxy benzophenone, and hydroxy Benzophenones such as dodecyloxybenzophenone, hydroxymethoxysulfobenzophenone and bis (methoxyhydroxybenzoylphenyl) methane; (hydroxymethylphenyl) benzotriazole, (hydroxybutylphenyl) benzotriazole, ( Hydroxydibutylphenyl) benzotriazole, (hydroxybutylmethylphenyl) chlorobenzotriazole, (hydroxydibutylphenyl) chlorobenzotriazole, (hydroxydiazylphenyl) benzotriazole and [hydroxy (tetrahydro) Benzotriazoles such as loftalimide methyl) methylphenyl] benzotriazole; ethylhexyl cyano diphenyl acrylate and ethyl cyano diphenyl acrylate A cyano-acrylate; and the like can be used hindered amines.

As the leveling agent, for example, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, acrylic copolymerization Known ones such as water, methacrylic copolymers, polyether modified polymethylalkylsiloxanes, acrylic acid alkylester copolymers, methacrylic acid alkylester copolymers, lecithin, or mixtures thereof can be used.

As an antifoamer, silicone oil etc. can be used, for example.

Examples of the thickener include polyalkyl methacrylate homopolymers, copolymers of different methacrylate esters, copolymers of methacrylic acid esters and acrylate esters, acrylic rubbers, polyesters, polyvinyl chlorides, polystyrenes, cellulose esters, Polyalkyl-α-cyanoacrylate, ethylene-vinyl acetate copolymer, and the like. These thickeners may be contained alone in the curable composition of the present invention, or may contain a mixture of two or more thereof. As a specific compound, for example, as a polyalkyl methacrylate homopolymer, polymethyl methacrylate (it abbreviates as PMMA below), polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, etc. are mentioned. have. As a compound used as a raw material of the copolymer of a heterogeneous methacrylic acid ester, and a copolymer of methacrylic acid ester and an acrylic acid ester, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, meta Methacrylic acid-iso-propyl, methacrylic acid-n-butyl, methacrylic acid-iso-butyl, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, acrylic acid-iso-propyl, acrylic acid-n-butyl, acrylic acid-iso -Butyl etc. are mentioned.

Flame retardants include known inorganic or organic flame retardants such as aluminum hydroxide, antimony oxide, perchloropentacyclodecane, tetrabromobisphenol A, pentabromophenol methacrylate, halogenated epoxy resins, 4-bromophenylmaleimide , Oligomers of 2, 4-dibromophenyl maleimide, 2, 4, 6-tribromophenyl maleimide, and bromophenyl maleimide can be used.

As the filler, inorganic fillers such as silica powder such as fused silica and crystalline silica, alumina, magnesium oxide (magnesia), wollastonite, mica, calcium carbonate, talc, glass and the like are preferably blended. These fillers can be used as the powder, particulate, flake or fibrous fillers or surface treated with a coupling agent. Moreover, what used organic fiber, such as testosterone, a vinylon, and an aromatic polyamide, as a twisted strand can be used.

As a plasticizer, For example, Phthalic acid ester, such as dibutyl phthalate and dioctyl phthalate; Phosphoric acid ester, such as tricresyl phosphate and diphenyl octyl phosphate; Dibutyl sebacate, dioctyl sebacate, di-2-ethylhexyl Dibasic acid ester, such as an adipate, etc. are used.

As the pigment, any pigments of acidic pigments, neutral pigments and basic pigments can be used. For example, barium sulfate or the like can be used as the acidic pigment, and titanium oxide, zinc oxide, amorphous silica, clay, kaolin, calcined kaolin, talc, satin white, plastic pigment, and the like can be used as the neutral pigment. As the calcium carbonate, aluminum hydroxide, barium carbonate, magnesium hydroxide and the like can be used.

As an antistatic agent, the various cationic compounds which have cationic groups, such as a quaternary ammonium salt, a pyridinium salt, and a 1st-3rd amino group; Anionic groups, such as a sulfonate group, a sulfate ester base, a phosphate ester base, and a phosphonate group, Warm compounds; amphoteric compounds such as amino acid and amino sulfate esters; nonionic compounds such as amino alcohols, glycerin and polyethylene glycol; organic metal compounds such as alkoxides of tin and titanium, and their acetylacetonate salts and the like. Metal chelate compounds and the like can be used. Moreover, the compound which carried out high molecular weight of the compound mentioned above can also be used. Moreover, polymerizability, such as an organometallic compound, such as a coupling agent which has a tertiary amino group, a quaternary ammonium group, or a metal chelate part, and has a monomer or oligomer which can superpose | polymerize by ionizing radiation, and a functional group which can superpose | polymerize by ionizing radiation, etc. The compound can also be used as an antistatic agent.

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene; ester solvents such as methyl acetate, ethyl acetate and n-propyl acetate; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, styrene, and propylene. Polymerizable monomers; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone; diethyl ether, tetrahydrofuran, 1, 2-dimethoxyethane, 1, Ether solvents such as 4-dioxane; nitrile solvents such as acetonitrile and benzonitrile; dimethyl sulfoxide; phosphate amide solvents such as hexamethylphosphoramide (HMPT) and hexamethylphosphoramide (HMPA); Can be mentioned. Moreover, only 1 type may be used as a solvent and 2 or more types of mixtures can be used.

The silylated polybutadiene of the present invention can be cured by heating, light irradiation or the like together with a polymerization initiator. Therefore, the curable composition of this invention can be hardened by heat processing, light irradiation treatment, etc., for example.

It does not specifically limit as a method of heating the curable composition of this invention, Conventionally well-known heating methods, such as a heater, can be used.

Ultraviolet rays, visible light, X-rays, electron beams, etc. can be used for the light irradiation process of the curable composition of this invention, for example.

It does not specifically limit as a method of irradiating visible light, For example, the method of using an incandescent bulb, a fluorescent lamp, etc. are mentioned. Moreover, it does not specifically limit as a method of irradiating an ultraviolet-ray, For example, a metal halide lamp, a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, etc. are used as an electrode system, an excimer lamp, a metal halide lamp, etc. as an electrodeless system. And the like may be used. When using an ultraviolet-ray, the wavelength range is not specifically limited, 150 nm-400 nm are preferable and 200 nm-380 nm are more preferable. As an atmosphere to irradiate ultraviolet rays, an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere having a reduced oxygen concentration is preferable, but can also be a normal air atmosphere. Irradiation atmosphere temperature can be 10-200 degreeC normally.

It is preferable to use an ultraviolet-ray for the light irradiation process of the curable composition of this invention. Since ultraviolet rays have high energy, the curing reaction of the curable composition can be accelerated by irradiating the curable composition of the present invention with the ultraviolet ray, and the amount of unreacted curable composition in the cured product can be increased. Can be reduced.

The hardened state of the obtained hardened | cured material can be measured using a Fourier transform infrared spectroscopy apparatus, a photochemical reaction calorimeter, etc. By irradiating a hardened state using these apparatus, hardening conditions (heating time, heating time, etc. of light irradiation time, light intensity, etc.) for completely hardening hardened | cured material can be selected suitably.

Example

Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example.

[Example 1]

1,2-polybutadiene (NISSO-PB B-1000 (number average molecular weight (Mn): 1300, 1, 2-bond content: 83%, manufactured by Nippon Soda Co., Ltd.)) in a flask with a cooling tube under a nitrogen stream. To a 1,2-polybutadiene solution in which 30.0 g was dissolved in 42.0 g of toluene, a mixture of 2.82 g of triphenylsilane and 51.1 g of toluene was added and stirred with a mechanical stirrer. 0.29g of platinum catalyst (3% Pt-CTS toluene solution (made by NE Chemcat Co., Ltd.)) was added to this solution, and it stirred, maintaining internal temperature at 100 degreeC-110 degreeC. After confirming the disappearance of triphenylsilane by ¹ H-NMR, the solvent was removed by concentration under reduced pressure to obtain 28.50 g of triphenylsilylated polybutadiene. As a result of measuring the microstructure by NMR method, the silylation rate of the obtained triphenyl silylated polybutadiene was 2%.

[Example 2]

1,2-polybutadiene (NISSO-PB B-1000 (number average molecular weight (Mn): 1300, 1, 2-bond content rate: 83%, manufactured by Nippon Soda Co., Ltd.)) in a flask with a cooling tube under a nitrogen stream. To a 1,2-polybutadiene solution in which 30.0 g was dissolved in 39.7 g of toluene, a mixture of 6.98 g of triphenylsilane and 39.9 g of toluene was added and stirred with a mechanical stirrer. 0.29g of platinum catalyst (3% Pt-CTS toluene solution (made by NE Chemcat Co., Ltd.)) was added to this solution, and it stirred, maintaining internal temperature at 100 degreeC-110 degreeC. After confirming the disappearance of triphenylsilane by ¹ H-NMR, the solvent was removed by concentration under reduced pressure to obtain 27.9 g of triphenylsilylated polybutadiene. As a result of measuring the micro structure by NMR method, the silylation rate of the obtained triphenyl silylated polybutadiene was 5%.

[Example 3]

1,2-polybutadiene (NISSO-PB B-1000 (number average molecular weight (Mn): 1300, 1, 2-bond content rate: 83%, manufactured by Nippon Soda Co., Ltd.)) in a flask with a cooling tube under a nitrogen stream. To a 1,2-polybutadiene solution in which 30.0 g was dissolved in 42.0 g of toluene, a mixture of 13.94 g of triphenylsilane and 43.2 g of toluene was added and stirred with a mechanical stirrer. 0.27g of platinum catalyst (3% Pt-CTS toluene solution (made by NE Chemcat Co., Ltd.)) was added to this solution, and it stirred, maintaining the internal temperature at 100 degreeC-110 degreeC. After confirming the disappearance of triphenylsilane by ¹ H-NMR, the solvent was removed by concentration under reduced pressure to obtain 27.47 g of triphenylsilylated polybutadiene. As a result of measuring the microstructure by NMR method, the silylation rate of the obtained triphenyl silylated polybutadiene was 9%.

[Example 4]

1,2-polybutadiene (NISSO-PB B-1000 (number average molecular weight (Mn): 1300, 1, 2-bond content rate: 83%, manufactured by Nippon Soda Co., Ltd.)) in a flask with a cooling tube under a nitrogen stream. To a 1,2-polybutadiene solution in which 20.0 g was dissolved in 21.0 g of toluene, a mixture of 18.8 g of triphenylsilane and 43.2 g of toluene was added and stirred with a mechanical stirrer. After adding 0.60g of a platinum catalyst (3% Pt-CTS toluene solution (made by NE Chemcat Co., Ltd.)) to this solution, it stirred, maintaining internal temperature at 100 degreeC-110 degreeC. After confirming the loss of triphenylsilane by ¹ H-NMR, the solvent was removed by concentration under reduced pressure to obtain 18.0 g of triphenylsilylated polybutadiene. As a result of measuring the microstructure by NMR method, the silylation rate of the obtained triphenyl silylated polybutadiene was 21%.

EXAMPLE 5

1,2-polybutadiene (NISSO-PB B-1000 (number average molecular weight (Mn): 1300, 1, 2-bond content rate: 83%, manufactured by Nippon Soda Co., Ltd.)) in a flask with a cooling tube under a nitrogen stream. 6.06 g of triphenylsilane was added to the 1, 2- polybutadiene solution which melt | dissolved 3.60g in 10.61g of toluene, and stirred with the mechanical stirrer. After adding 0.06g of a platinum catalyst (3% Pt-CTS toluene solution (made by NE Chemcat Co., Ltd.)) to this solution, it stirred, maintaining internal temperature at 100 degreeC-110 degreeC. After confirming the disappearance of triphenylsilane by ¹ H-NMR, the solvent was removed by concentration under reduced pressure to obtain 9.45 g of triphenylsilylated polybutadiene. As a result of measuring the micro structure by NMR method, the silylation rate of the obtained triphenyl silylated polybutadiene was 37%.

[Comparative Example 1]

1,2-polybutadiene (NISSO-PB B-1000 (number average molecular weight (Mn): 1300, 1, 2-bond content rate: 83%, manufactured by Nippon Soda Co., Ltd.)) in a flask with a cooling tube under a nitrogen stream. To a 1,2-polybutadiene solution in which 40.0 g was dissolved in 42.7 g of toluene, a mixture of 41.4 g of triethylsilane and 36.6 g of toluene was added and stirred with a mechanical stirrer. 0.032g of platinum catalyst (hexachloro platinum (VI) acid hexahydrate) was added to this solution, and it stirred, maintaining internal temperature at 100 degreeC-110 degreeC. After adding the solution which melt | dissolved 11.37g of triethylsilane in 20.23g of toluene on the way, stirring was continued, maintaining internal temperature 100 degreeC-110 degreeC. After confirming the progress of the reaction by ¹ H-NMR, the solvent and excess triethylsilane were removed by concentration under reduced pressure to obtain 18.0 g of triethylsilylated polybutadiene. As a result of measuring the microstructure by NMR method, the silylation rate of the obtained triethylsilylated polybutadiene was 4%.

[Comparative Example 2]

1,2-polybutadiene (NISSO-PB B-1000 (number average molecular weight (Mn): 1300, 1, 2-bond content rate: 83%, manufactured by Nippon Soda Co., Ltd.)) in a flask with a cooling tube under a nitrogen stream. To a 1,2-polybutadiene solution in which 30.1 g was dissolved in 40.0 g of toluene, a mixture of 6.2 g of triethylsilane and 40.8 g of toluene was added and stirred with a mechanical stirrer. 0.31g of platinum catalyst (3% Pt-CTS toluene solution (made by NE Chemcat Co., Ltd.)) was added to this solution, and it stirred, maintaining internal temperature at 100 degreeC-110 degreeC. In the meantime, 17.4 g of triethylsilane and 11.4 g of toluene were added, and stirring was continued, maintaining internal temperature at 100 degreeC-110 degreeC. After confirming the progress of the reaction by ¹ H-NMR, the solvent and excess triethylsilane were removed by concentration under reduced pressure to obtain 29.4 g of triethylsilylated polybutadiene. As a result of measuring the microstructure by NMR method, the silylation rate of the obtained triethylsilylated polybutadiene was 9%.

[Comparative Example 3]

1,2-polybutadiene (NISSO-PB B-1000 (number average molecular weight (Mn): 1300, 1, 2-bond content rate: 83%, manufactured by Nippon Soda Co., Ltd.)) in a flask with a cooling tube under a nitrogen stream. To a 1,2-polybutadiene solution in which 30.5 g was dissolved in 70.1 g of toluene, a mixture of 50.8 g of triethylsilane and 16.1 g of toluene was added and stirred with a mechanical stirrer. After adding 0.031g of platinum catalyst (hexachloro platinum (VI) acid hexahydrate) to this solution, it stirred, maintaining internal temperature at 100 degreeC-110 degreeC. On the way, 8.31g of triethylsilane and 0.016g of platinum catalysts (hexachloro platinum (VI) acid hexahydrate) were added, and stirring was continued, maintaining internal temperature at 100 degreeC-110 degreeC. After confirming the progress of the reaction by ¹ H-NMR, the solvent and excess triethylsilane were removed by concentration under reduced pressure to obtain 25.4 g of triethylsilylated polybutadiene. As a result of measuring the microstructure by NMR method, the silylation rate of the obtained triethylsilylated polybutadiene was 17%.

[Test Example 1] (shear test)

1 g of triphenylsilylated polybutadiene (silylation rate 2%) and 0.02 g of percumyl D (manufactured by Nichi Oil Co., Ltd.) obtained in Example 1 were mixed well (composition A). 0.01 g of composition A was uniformly applied to 1.25 cm and 2.5 cm in width of the iron plate having a length of 10 cm, a width of 2.5 cm, and a thickness of about 1 mm. Another iron plate was superimposed on the iron plate to which the composition A was applied, and the bonded iron plate was heated in an oven for 3 hours at 110 ° C, and further heated at 150 ° C for 3 hours, and then allowed to cool to room temperature.

Using Shimadzu Corporation AGS-J (5 kN), peeling was performed at a tensile speed of 10 mm / min, with a holding section distance of the bonded iron plate being 125 mm. The maximum value (maximum stress MPa) of the stress which generate | occur | produced at this time was measured. Table 1 shows the results.

[Test Examples 2 to 4] (shear test)

Instead of the triphenylsilylated polybutadiene obtained in Example 1, except that the triphenylsilylated polybutadiene (5%, 9%, 21% silylation rate) obtained in Examples 2 to 4 was used in the same manner as in Test Example 1 The maximum stress (MPa) at the time of peeling the iron plate bonded by each triphenyl silylated polybutadiene was measured. Table 1 shows the results.

[Comparative Test Example 1] (Shear Test)

The test was used in place of the triphenylsilylated polybutadiene obtained in Example 1 except that NISSO-PB B-1000 (number average molecular weight (Mn): 1300, 1, 2-bond content: 83%, manufactured by Nippon Soda Co., Ltd.) was used. In the same manner as in Example 1, the maximum stress (MPa) at the time of peeling the iron plate bonded with each triphenylsilylated polybutadiene was measured. Table 1 shows the results.

Comparative Test Examples 2 to 4 (Shear Test)

Instead of the triphenylsilylated polybutadiene obtained in Example 1, except that triethylsilylated polybutadiene (4%, 9%, 17% silylation rate) obtained in Comparative Examples 1 to 3 was used in the same manner as in Test Example 1 The maximum stress (MPa) at the time of peeling the iron plate bonded by each triphenyl silylated polybutadiene was measured. Table 1 shows the results.

[Test Examples 5 to 7] (shear test)

The maximum stress (MPa) in the same manner as in Test Examples 1 to 3, except that an aluminum plate having a length of 10 cm, a width of 2.5 cm, and a thickness of about 1 mm was used instead of a steel plate having a length of 10 cm, a width of 2.5 cm, and a thickness of about 1 mm. Was measured. Table 1 shows the results.

Comparative Test Example 5 (Shear Test)

The maximum stress (MPa) was obtained in the same manner as in Comparative Test Example 1 except that an aluminum plate having a length of 10 cm, a width of 2.5 cm, and a thickness of about 1 mm was used instead of a steel plate having a length of 10 cm, a width of 2.5 cm, and a thickness of about 1 mm. Measured. Table 1 shows the results.

Type of plate Silane compound Silylation rate (%) Max stress (MPa) Test Example 1



iron plate



Triphenylsilane

2 2.58 Test Example 2 5 10.1 Test Example 3 9 4.36 Test Example 4 21 2.84 Comparative Test Example 1 - 0 0.70 Comparative Test Example 2
Triethylsilane
4 0.96 Comparative Test Example 3 9 1.05 Comparative Test Example 4 17 0.64 Test Example 5
Aluminum plate


Triphenylsilane
2 3.15 Test Example 6 5 5.67 Test Example 7 9 4.92 Comparative Test Example 5 - 0 1.25

As a result, in Test Examples 1 to 4 using the iron plate and Comparative Test Examples 1 to 4, in Comparative Examples 1 to 4 using the curable composition containing the silylated polybutadiene of the present invention, comparison was made using polybutadiene which was not silylated. The maximum stress at the time of peeling the bonded iron plate was clearly larger than Test Example 1 and Comparative Test Examples 2-4 using triethylsilylated polybutadiene. In addition, even in the case of using an aluminum plate, in Comparative Examples 5 to 7 using the curable composition containing the silylated polybutadiene of the present invention having a silylation rate of 2 to 9%, Comparative Test Example 5 using polybutadiene not silylated Moreover, the maximum stress at the time of peeling the bonded aluminum plate was clearly large. From these results, it is clear from the curable composition containing the silylated polybutadiene of this invention that the hardened | cured material excellent in the shear force is obtained.

[Test Example 8] Refractive Index Evaluation Test

(Preparation of Curable Composition)

4 g of triphenylsilylated polybutadiene (silylation rate 2%) obtained in Example 1 was dissolved in 36 g of methyl isobutyl ketone. 0.16 g of a brand name Irgacua 907 (made by BASF) was added to this solution, and the curable composition was prepared.

(Creation of a Cured Thin Film)

It processed by the dip coat method so that it might become 500 nm on 1 cm x 2 cm silicon wafer. After drying for 3 minutes at 80 degreeC, UV curing was performed with the belt conveyor type UV irradiator. On the conditions of high pressure mercury lamp output: 120 W / cm, UV lamp distance: 9.8 cm, UV irradiation was performed so that the accumulated irradiation amount in 365 nm might be 2000 mJ / cm <^2> , and the hardened thin film was obtained.

(Refractive index measurement)

The refractive index at 400 nm and 550 nm was measured using the spectroscopic ellipsometry (made by J. A. Woolam Japan). Table 2 shows the results.

[Test Examples 9 to 11] Refractive Index Evaluation Test

In the same manner as in Test Example 8, except that the triphenylsilylated polybutadiene (silylation rate 9%, 21%, 37%) obtained in Examples 3 to 5 was used instead of the triphenylsilylated polybutadiene obtained in Example 1. The refractive index of the cured thin film was measured. Table 2 shows the results.

Comparative Test Example 6

Instead of the triphenylsilylated polybutadiene obtained in Example 1, the refractive index of the cured thin film was measured in the same manner as in Test Example 8 except that NISSO-PB B-1000 (0% silylation rate) was used. Table 2 shows the results.

Silylation rate (%)
Refractive index 400 nm 550 nm Comparative Test Example 6 0 1.522 1.500 Test Example 8 2 1.538 1.515 Test Example 9 9 1.621 1.592 Test Example 10 21 1.670 1.637 Test Example 11 37 1.634 1.600

As shown in Table 2, in Test Examples 8 to 11 using the cured thin film derived from the curable composition containing the silylated polybutadiene of the present invention having a silylation rate of 2 to 37%, the curability containing polybutadiene not silylated The refractive index was higher in all of 400 nm and 550 nm than the comparative test example 6 which used the cured thin film derived from a composition. In particular, in Test Examples 10 and 11 using a cured thin film derived from silylated polybutadiene having a silylation rate of 21 to 37%, the refractive index was remarkably high in all of 400 nm and 550 nm.

Industrial availability

The curable composition containing the silylated polybutadiene of the present invention has excellent shear force as the cured product. For this reason, the said curable composition is useful as various adhesive agents, such as a solvent adhesive and a 2-liquid acrylic adhesive, thin film materials, such as various coating films, etc. Moreover, the thin film obtained by hardening | curing the curable composition containing silylated polybutadiene has high refractive index. In view of the above, the present invention is very useful industrially.

Claims (8)

In formula (I)
However,

(In formula (I), R <^1> , R <^2> and R <^3> respectively independently represents an aryl group, an alkyl group, or an aralkyl group which has an unsubstituted or substituent. However, at least 1 is an R <^1> -R <^3> A silylated polybutadiene containing a repeating unit represented by an aryl group or an aralkyl group.). The method according to claim 1,
The silylated polybutadiene containing the repeating unit represented by said formula (I) in 1-50 mol% among all the repeating units. 3. The method according to claim 1 or 2,
A silylated polybutadiene obtained by silylating a polybutadiene composed of a repeating unit represented by 75 to 100 mol% of the following formula (II) and a repeating unit represented by 0 to 25 mol% of the following formula (III).
[Figure 2]

The method according to any one of claims 1 to 3,
A silylated polybutadiene having a number average molecular weight of 500 to 10,000. The silylated polybutadiene and polymerization initiator of any one of Claims 1-4 are contained, The curable composition characterized by the above-mentioned. Hardened | cured material obtained by hardening | curing the curable composition of Claim 5. The silylated polybutadiene and polymerization initiator of any one of Claims 1-4 are contained, The adhesive agent characterized by the above-mentioned. The silylated polybutadiene and polymerization initiator of any one of Claims 1-4 are contained, The composition for thin film formation characterized by the above-mentioned.